低温固体氧化物燃料电池的阳极/电解质/阴极膜组件的研究

In view of key device of the low temperature solid oxide fuel cell (SOFCs) of having the strategic significance, the project create anode/ electrolyte/cathode film module of SOFCs for lower than 500℃. The new rare earth doped CeO2 films are prepared with anodic oxidation method, and cerium and rare earth elements as raw materials and dopants respectively. The film is composed by the porous nano-straight holes and the dense layer. After sintering dense layers of two the films, form the rare earth doped CeO2 film of the electrolyte and electrode skeleton as one. Plating or filling the electrode skeleton film with the catalysts form anode/electrolyte/ cathode film module. The influence laws of preparation conditions on the structure, thickness and conductivity performance of the rare earth doped CeO2 film, and on the electrochemical properties of the anode/electrolyte/cathode film module are explored. The relationships among the composition, structure and performance and action mechanism of rare earths are explored, providing a theoretical basis for the development of new film cell. The economic anodic oxidation method and rare earths are used in preparing the anode/electrolyte/cathode film module, saving energy and reducing the preparation cost, and changing the resource advantage to economic advantage. SOFCs of using the film module may direct use natural gas and methane as fuel, may achieve miniaturization and lightweight.

针对具有战略意义的低温固体氧化物燃料电池(SOFCs)的关键器件，本项目创制用于低于500℃SOFCs的阳极/电解质/阴极膜组件。用阳极氧化法、铈为原料、稀土作掺杂剂，制备上面是多纳米直孔下面是致密层的新型稀土掺杂CeO2膜，将2块该膜的致密层烧结，形成电解质与电极骨架为一体的稀土掺杂CeO2膜，将催化剂电镀或填充在电极骨架膜中，获得阳极/电解质/阴极膜组件。探索制备条件对该稀土掺杂CeO2膜的结构、厚度和导电率等性能影响的规律，及其对该膜组件电化学性能影响的规律；研究该膜组件组成、结构、特性之间的构效关系，阐明稀土的作用本质。为研制新型膜电池提供理论依据。采用经济的阳极氧化法和稀土制备性能优良的阳极/电解质/阴极膜组件，可大幅度节能及降低制备成本，对我国变资源优势为经济优势具有重大意义。该膜组件组装的SOFCs可直接利用天然气和甲烷为燃料，实现SOFCs的小型化和轻量化。

本项目完成了计划研究任务。针对具有战略意义的低温固体氧化物燃料电池(SOFCs)的关键器件，创制出了用于500℃SOFCs的Ni-RCC/RCC/RCC-BSCF膜组件。用阳极氧化法、铈为原料、稀土作掺杂剂，创制出了上面是多纳米直孔下面是致密层的新型RE掺杂CeO2膜，电解质与电极骨架为一体的Gd掺杂CeO2膜、RE/Ca共掺杂CeO2膜，发明了两面为多纳米直孔中间为致密层的CeO2膜、电解质与电极骨架为一体的RE掺杂CeO2膜和RE/Ca共掺杂CeO2膜、阳极材料和电解质与电极骨架为一体的RE/Ni共掺杂CeO2膜、RE/Ni/Cu共掺杂CeO2膜、RE/Ca/Ni共掺杂CeO2膜、RE/Ca/Ni/Cu共掺杂CeO2膜。采用填充法制得了Ni-RCC/RCC/RCC-BSCF膜组件。探索了制备条件对上述创制的膜的结构、厚度和电导率等性能影响的规律，及其对该膜组件的电化学性能影响的规律；研究出了该膜组件组成、结构、特性之间的构效关系，阐明了稀土的作用本质。为研制新型膜电池提供了理论依据。上述创制的膜的电导率(500℃)和多孔膜厚h(单面)依次分别为：1.01×10-2～1.39×10-2、1.08×10-2～1.36×10-2、2.56×10-2～8.80×10-2、4.9×10-5、9.80×10-3～1.37×10-2、2.47×10-2～8.59×10-2、5.22×10-3～7.32×10-2、4.52×10-3～6.30×10-2、6.39×10-2～1.21×10-1、5.81×10-2～1.09×10-1S•cm-1和15～97、97、16～107、11～97、15～97、16～107、15～106、18～112、16～109、19～121μm。由Ni-RCC/RCC/RCC-BSCF膜组件组装的电池的开路电压V和最大输出功率P分别为0.81～1.02V和0.76～1.02W/cm2。电池中的RE对V和P影响次序分别为：Sm>Dy>Er>Nd>Pr>Gd>La和Gd>Sm>La>Nd>Dy>Er>Pr。采用经济的阳极氧化法和稀土制备性能优良的膜组件，可大幅度节能及降低制备成本。该膜组件组装的SOFCs可直接利用天然气和甲烷为燃料，实现SOFCs的小型化和轻量化。申请了8项中国发明专利，已授权4项，发表了19篇文章，SCI、EI检索的文章18篇。